Deformation and crystallization of Zr-based amorphous alloys in homogeneous flow regime

The purpose of this study is to experimentally investigate the interaction of inelastic deformation and microstructural changes of two Zr-based bulk metallic glasses (BMGs): Zr41.25Ti13.75Cu12.5Ni10Be22.5 (commercially designated as Vitreloy 1 or Vit1) and Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy 4, Vit4). High-temperature uniaxial compression tests were performed on the two Zr alloys at various strain rates, followed by structural characterization using differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Two distinct modes of mechanically induced atomic disordering in the two alloys were observed, with Vit1 featuring clear phase separation and crystallization after deformation as observed with TEM, while Vit4 showing only structural relaxation with no crystallization. The influence of the structural changes on the mechanical behaviors of the two materials was further investigated by jump-in-strain-rate tests, and flow softening was observed in Vit4. A free volume theory was applied to explain the deformation behaviors, and the activation volumes were calculated for both alloys.

Molecular modelling of saccharide-lipid interactions

Certain saccharides, including trehalose, sucrose and glucose, stabilize lipid bilayers against dehydration. It has been suggested that these saccharides replace waters of hydration as the system is dried, thereby maintaining the headgroups at their hydrated spacing. The lipid acyl chains consequently have sufficient free volume to remain in the liquid crystallines state, and the processes that disrupt membrane integrity are inhibited. Initial molecular graphic investigations of a model trehalose/DMPC system supported this idea (Chandrasekhar, I. and Gaber, B.P. (1988) J. Biomol. Stereodyn, 5, 1163–1171). We have extended these studies to glucose and sucrose. A set of AMBER potential parameters has been established that reproduce simple saccharide conformations, including the anomeric effect. Extensive energy minimizations have been conducted on all three systems. The saccharide-lipid interaction energies become less stable in the order trehalose

On the water-induced critical double point in a polymer solution: the role of isotopic substitution

This paper examines the effect of substitution of water by heavy water in a polymer solution of polystyrene (molecular weight = 13000) and acetone. A critical double point (CDP), at which the upper and the lower partially-miscible regions merge, occurs at nearly the same coordinates as for the system [polystyrene + acetone + water]. The shape of the critical line for [polystyrene + acetone + heavy water] is highly asymmetric. An explanation for the occurrence of the water-induced CDP in [polystyrene + acetone] is advanced in terms of the interplay between contact energy dissimilarity and free-volume disparity of the polymer and the solvent. The question of the possible existence of a one-phase hole in an hourglass phase diagram is addressed in [polystyrene + acetone + water]. Our data exclude such a possibility.

Increased time-dependent room temperature plasticity in metallic glass nanopillars and its size-dependency

Room temperature, uniaxial compression creep experiments were performed on micro-/nano-sized pillars (having diameters in the range of 250-2000 nm) of a Zr-based bulk metallic glass (BMG) to investigate the influence of sample size on the time-dependent plastic deformation behavior in amorphous alloys. Experimental results reveal that plastic deformation indeed occurs at ambient temperature and at stresses that are well below the nominal quasi-static yield stress. At a given stress, higher total strains accrue in the smaller specimens. In all cases, plastic deformation was found to be devoid of shear bands, i.e., it occurs in homogeneous manner. The stress exponent obtained from the slope of the linear relation between strain rate and applied stress also shows a strong size effect, which is rationalized in terms of the amount of free volume created during deformation and the surface-to-volume ratio of the pillar. (C) 2012 Elsevier Ltd. All rights reserved.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

On the strain rate sensitivity of plastic flow in metallic glasses

The nanoindentation technique was employed to examine the strain rate sensitivity, m, and its dependence on the structural state of a Zr-based bulk metallic glass (BMG). The free volume content in the BMG was varied by examining samples in the as-cast (AC), shot-peened (SP), and structurally relaxed (SR) states. Hardness values measured at different loading rates and over a temperature range of 300-423 K as well as the strain-rate jump tests conducted in the quasi-static regime at room temperature, show that m is always negative. All the load-displacement (P-h) curves in this temperature regime exhibit serrated load-displacement responses, indicating that the shear band mediated inhomogeneous plastic flow governs deformation. Such localization of flow and associated softening is the raison d'etre for the negative m. Significant levels of pile-up around the indents were also noted. The order in the average values of hardness, pile-up heights, and the displacement bursts on the P-h curves was always such that SR > AC > SP, which is also the order of increasing free volume content. These observations were utilized to discuss the reasons for the negative strain rate sensitivity, and its dependence on the structural state of metallic glasses. It is suggested that the positive values of m reported in the literature for them are possibly experimental artefacts that arise due to large pile ups around the indents which lead to erroneous estimation in hardness values. (C) 2014 Elsevier B.V. All rights reserved.

Effect of structural relaxation on deformation behaviour of Zr-based metallic glass

Structural relaxation through isothermal annealing at tempertature below glass transition is conducted on Zr46.75Ti8.25Cu7.5Ni10Be27.5 (Vitreloy-4) bulk metallic glass. Defect concentration is correlated with the annealing time t according to differential scanning calorimetry thermalgrams. The effects of structural relaxation on mechanical properties and deformation behaviour are investigated by using instrumented nanoindentation. It is found that as-cast alloy exhibits pronounced serration flow during the loading process of nanoindentation, and the size and number of serrations decrease with the annealing time. The change of the deformation behaviour with structural relaxation is explained using a free volume model.

Behavior of Multiple Shear Bands in Zr-Based Bulk Metallic Glass

The deformation behavior of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass was studied by in situ scanning electron microscopy (SEM) quasi-static uniaxial compression tests at room temperature. Multiple shear bands were observed with a large plasticity. Microscopic examination demonstrates that slipping, branching and intersecting of multiple shear bands are the main mechanisms for enhancing the plasticity of this metallic glass. Additionally, nano/micro-scale voids and cracks at the intersecting sites of shear bands and preferential etching of shear bands were observed as well. These observations demonstrated that the formation of shear bands in bulk metallic glasses is resulted mainly from local free volume coalescence.

Characterization of Plastic Flow in Two Zr-Based Bulk Metallic Glasses

Plastic deformation behaviors of Zr65Al10Ni10CU15 and Zr52.5Al10Ni10Cu15Be12.5 bulk metallic glasses (BMGs) are studied by using the depth-sensing nanoindentation, microindentation and uniaxial compression. The Be-containing BMG exhibits a significantly improved overall plastic strain compared with the Be-free alloy during compressive tests. Both BMGs show a loading-rate-dependent serrated flow during nanoindentation measurements, but the Be-containing alloy exhibits a much lower critical loading rate for the disappearance of the serration than the Be-free BMG. The shear band patterns developed during plastic deformation are investigated by microindentation technique, wherein much higher shear band density is found in the Be-containing alloy than in the Be-free alloy, indicating an easier nucleation of shear bands in the former BMG. The difference in the plastic deformation behavior of the two BMGs can be explained by a free volume model.

Basic Mechanical Behaviors And Mechanics Of Shear Banding In Bmgs

In this paper, some basic mechanical behaviors of bulk metallic glasses (BMGs) were discussed. It can be found from the discussions that the mechanical behaviors of BMGs are mainly due to the formation and operation of shear bands in BMGs. Furthermore, the relevant mechanics of shear banding were investigated in the paper. The theoretical analysis of deformation coupling thermal softening and free volume creation softening demonstrates that the free volume creation and thermal softening can jointly promote the formation of shear bands in BMGs, and the observed post mortem. shear band width looks more like that governed by free volume creation. (C) 2007 Elsevier Ltd. All rights reserved.

Study Of Mechanical Properties Of Amorphous Copper With Molecular Dynamics Simulation

The formation and mechanical properties of amorphous copper are studied using molecular dynamics simulation. The simulations of tension and shearing show that more pronounced plasticity is found under shearing, compared to tension. Apparent strain hardening and strain rate effect are observed. Interestingly, the variations of number density of atoms during deformation indicate free volume creation, especially under higher strain rate. In particular, it is found that shear induced dilatation does appear in the amorphous metal.

The characterization of plastic flow in three different bulk metallic glass systems

Plastic deformation behaviors of Zr52.5Al10Ni10Cu15Be12.5, Mg65Cu25Gd10 and Pd43Ni10Cu27P20 bulk metallic glasses (BMGs) are studied by using the depth-sensing nanoindentation, macroindentation and uniaxial compression. The significant difference in plastic deformation behavior cannot be correlated to the Poisson's ratio or the ratio of shear modulus to bulk modulus of the three BMGs, but can be explained by the free volume model. It is shown that the nucleation of local shear band is easy and multiple shear bands can be activated in the Zr52.5Al10Ni10Cu15Be12.5 alloy, which exhibits a distinct plastic strain during uniaxial compression and less serrated flow during nanoindentation. (c) 2006 Elsevier B.V. All rights reserved.

Formation Mechanism Of Lamellar Chips During Machining Of Bulk Metallic Glass

The uniqThe unique lamellar chips formed in turning–machining of a Vit 1 bulk metallic glass (BMG) are found to be due to repeated shearband formation in the primary shear zone (PSZ). A coupled thermomechanical orthogonal cutting model, taking into account force, free volume and energy balance in the PSZ, is developed to quantitatively characterize lamellar chip formation. Its onset criterion is revealed through a linear perturbation analysis. Lamellar chip formation is understood as a self-sustained limit-cycle phenomenon: there is autonomous feedback in stress, free volume and temperature in the PSZ. The underlying mechanism is the symmetry breaking of free volume flow and source, rather than thermal instability. These results are fundamentally useful for machining BMGs and even for understanding the physical nature of inhomogeneous flow in BMGs.ue lamellar chips formed in turning–machining of a Vit 1 bulk metallic glass (BMG) are found to be due to repeated shearband.

Prediction Of Shear-Band Thickness In Metallic Glasses

We derive an explicit expression for predicting the thicknesses of shear bands in metallic glasses. The model demonstrates that the shear-band thickness is mainly dominated by the activation size of the shear transformation zone (STZ) and its activation free volume concentration. The predicted thicknesses agree well with the results of measurements and simulations. The underlying physics is attributed to the local topological instability of the activated STZ. The result is of significance in understanding the origin of inhomogeneous flow in metallic glasses. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

On the origin of shear banding instability in metallic glasses

To uncover the physical origin of shear-banding instability in metallic glass (MG), a theoretical description of thermo-mechanical deformation of MG undergoing one-dimensional simple shearing is presented. The coupled thermo-mechanical model takes into account the momentum balance, the energy balance and the dynamics of free volume. The interplay between free-volume production and temperature increase being two potential causes for shear-banding instability is examined on the basis of the homogeneous solution. It is found that the free-volume production facilitates the sudden increase in the temperature before instability and vice versa. A rigorous linear perturbation analysis is used to examine the inhomogeneous deformation, during which the onset criteria and the internal length and time scales for three types of instabilities, namely free-volume softening, thermal softening and coupling softening, are clearly revealed. The shear-banding instability originating from sole free-volume softening takes place easier and faster than that due to sole thermal softening, and dominates in the coupling softening. Furthermore, the coupled thermo-mechanical shear-band analysis does show that an initial slight distribution of local free volume can incur significant strain localization, producing a shear band. During such a localization process, the local free-volume creation occurs indeed prior to the increase in local temperature, indicating that the former is the cause of shear localization, whereas the latter is its consequence. Finally, extension of the above model to include the shear-induced dilatation shows that such dilatation facilitates the shear instability in metallic glasses.